High refractive index aromatic-based silyl monomers

ABSTRACT

Optically transparent, relatively high refractive index polymeric compositions and ophthalmic devices such as intraocular lenses, contact lenses and corneal inlays made therefrom are described herein. The preferred polymeric compositions are produced through the polymerization of one or more aromatic-based silyl monomers or the copolymerization of one or more aromatic-based silyl monomers with one or more aromatic or non-aromatic non-siloxy-based monomers, hydrophobic monomers or hydrophilic monomers.

This patent application is a divisional application of U.S. PatentApplication having Ser. No. 10/003,616, filed on Nov. 2, 2001, now U.S.Pat. No. 6,762,271.

FIELD OF THE INVENTION

The present invention relates to monomers useful in the manufacture, ofbiocompatible medical devices. More particularly, the present inventionrelates to aromatic-based silyl monomers capable of polymerization aloneor copolymerization with other monomers. Upon polymerization orcopolymerization, the subject monomers form polymeric compositionshaving desirable physical characteristics and refractive indices usefulin the manufacture of ophthalmic devices.

BACKGROUND OF THE INVENTION

Since the 1940's ophthalmic devices in the form of intraocular lens(IOL) implants have been utilized as replacements for diseased ordamaged natural ocular lenses. In most cases, an intraocular lens isimplanted within an eye at the time of surgically removing the diseasedor damaged natural lens, such as for example, in the case of cataracts.For decades, the preferred material for fabricating such intraocularlens implants was poly(methyl methacrylate), which is a rigid, glassypolymer.

Softer, more flexible IOL implants have gained in popularity in morerecent years due to their ability to be compressed, folded, rolled orotherwise deformed. Such softer IOL implants may be deformed prior toinsertion thereof through an incision in the cornea of an eye. Followinginsertion of the IOL in an eye, the IOL returns to its originalpre-deformed shape due to the memory characteristics of the softmaterial. Softer, more flexible IOL implants as just described may beimplanted into an eye through an incision that is much smaller, i.e.,less than 4.0 mm, than that necessary for more rigid IOLs, i.e., 5.5 to7.0 mm. A larger incision is necessary for more rigid IOL implantsbecause the lens must be inserted through an incision in the corneaslightly larger than the diameter of the inflexible IOL optic portion.Accordingly, more rigid IOL implants have become less popular in themarket since larger incisions have been found to be associated with anincreased incidence of postoperative complications, such as inducedastigmatism.

With recent advances in small-incision cataract surgery, increasedemphasis has been placed on developing soft, foldable materials suitablefor use in artificial IOL implants. In general, the materials of currentcommercial IOLs fall into one of three general categories: silicones,hydrophilic acrylics and hydrophobic acrylics.

In general, high water content hydrophilic acrylics, or “hydrogels,”have relatively low refractive indices, making them less desirable thanother materials with respect to minimal incision size. Low refractiveindex materials require a thicker IOL optic portion to achieve a givenrefractive power. Silicone materials may have a higher refractive indexthan high-water content hydrogels, but tend to unfold explosively afterbeing placed in the eye in a folded position. Explosive unfolding canpotentially damage the corneal endothelium and/or rupture the naturallens capsule and associated zonules. Low glass transition temperaturehydrophobic acrylic materials are desirable because they typically havea high refractive index and unfold more slowly and more controllablythan silicone materials. Unfortunately, low glass transition temperaturehydrophobic acrylic materials, which contain little or no waterinitially, may absorb pockets of water in vivo causing light reflectionsor “glistenings.” Furthermore, it may be difficult to achieve idealfolding and unfolding characteristics due to the temperature sensitivityof some acrylic polymers.

Because of the noted shortcomings of current polymeric materialsavailable for use in the manufacture of ophthalmic implants, there is aneed for stable, biocompatible polymeric materials having desirablephysical characteristics and refractive indices.

SUMMARY OF THE INVENTION

Soft, foldable, high refractive index, high elongation polymericcompositions of the present invention are produced through thepolymerization or copolymerization of aromatic-based silyl monomers. Thesubject monomers are synthesized through a multi-step reaction scheme.The polymeric compositions produced from the silyl monomers have idealphysical properties for the manufacture of ophthalmic devices. Thepolymeric compositions of the present invention are transparent, ofrelatively high strength for durability during surgical manipulations,of relatively high elongation, of relatively high refractive index andare biocompatible. The subject polymeric compositions are particularlywell suited for use as intraocular lens (IOLs) implants, contact lenses,keratoprostheses, corneal rings, corneal inlays and the like.

Preferred aromatic-based silyl monomers for use in preparing thepolymeric compositions of present invention have the generalizedstructure represented by Formula 1 below,

wherein R is a polymerizable group; X is selected from the groupconsisting of C₁₋₁₀ alkylene, C₁₋₁₀ alkyleneoxy, C₆₋₃₆ arylene, andC₆₋₃₆ aryleneoxy; and the R₁ groups may be the same or differentselected from the group consisting of C₁₋₁₀ alkyl, C₁₋₂₀ cycloalkyl,C₆₋₃₆ aryl, C₆₋₃₆ aryl ether, C₆₋₃₆ heterocycle, C₆₋₃₆ heterocycle withone or more substituents, C₁₋₁₀ alkyl ether and C₆₋₃₆ aryloxy.

Accordingly, it is an object of the present invention to providetransparent, polymeric compositions having desirable physicalcharacteristics for the manufacture of ophthalmic devices.

Another object of the present invention is to provide polymericcompositions of relatively high refractive index.

Another object of the present invention is to provide polymericcompositions suitable for use in the manufacture of intraocular lensimplants.

Another object of the present invention is to provide polymericcompositions that are biocompatible.

Another object of the present invention is to provide polymericcompositions suitable for use as contact lens materials.

Still another object of the present invention is to provide polymericcompositions that are economical to produce.

These and other objectives and advantages of the present invention, someof which are specifically described and others that are not, will becomeapparent from the detailed description and claims that follow.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to novel aromatic-based silyl monomerssynthesized through a three-step reaction scheme. The subjectaromatic-based silyl monomers are useful in the production ofbiocompatible polymeric compositions. The subject polymeric compositionshave particularly desirable physical properties. The subject polymericcompositions have a relatively high refractive index of approximately1.45 or greater and relatively high elongation of approximately 100percent or greater. Accordingly, the subject polymeric compositions areideal for use in the manufacture of ophthalmic devices. Thearomatic-based silyl monomers of the present invention are generallyrepresented by Formula 1 below:

wherein R is a polymerizable group selected from the group consisting ofmethacrylate, acrylate, acrylamido, methacrylamido, styryl, itaconate,fumaroyl, vinyl, vinyloxy, vinyl carbamate and vinyl carbonate; X isselected from the group consisting of C₁₋₁₀ alkylene, such as forexample but not limited to methylene, trimethylene or heptamethylene,C₁₋₁₀ alkyleneoxy, such as for example but not limited to ethyleneoxy,butyleneoxy or octyleneoxy, C₆₋₃₆ arylene, such as for example but notlimited to phenylene or naphthylene and C₆₋₃₆ aryleneoxy, such as forexample but not limited to phenyleneoxy or naphthyleneoxy; and the R₁groups may be the same or different selected from the group consistingof C₁₋₁₀ alkyl such as for example but not limited to methyl, propyl orpentyl but preferably propyl for increased stability, C₁₋₂₀ cycloalkylsuch as for example but not limited to cyclohexyl or cycloheptyl, C₆₋₃₆aryl such as for example but not limited to phenyl or naphthyl, C₆₋₃₆aryl ether such as for example but not limited to phenyl ether ornaphthyl ether, C₆₋₃₆ heterocycle such as for example but not limited topyridine, quinoline, furan or thiophene but preferably pyridine toincrease refractive index, C₆₋₃₆ heterocycle such as those describedabove with one or more substituents such as for example but not limitedto chlorine, fluorine, amine, amide, ketone or C₁₋₃ alkyl such as forexample methyl or propyl, C₆₋₃₆ aryloxy such as for example but notlimited to phenyloxy or naphthyloxy and C₁₋₁₀ alkyl ethers such as forexample methyl ether or propyl ether.

Examples of aromatic-based silyl monomers of the present inventioninclude for example but are not limited to1-methacryloyloxypropyldimethylphenylsilane,1-methacryloyloxypropyldiphenylmethylsilane and1-methacryloyloxypropyltriphenylsilane.

Aromatic-based silyl monomers of the present invention may besynthesized through a three-step reaction scheme as represented inScheme 1 below:

One or more aromatic-based silyl monomers of the present inventionproduced as described above may be polymerized alone or copolymerizedwith other monomers. One or more of the subject silyl monomers may becopolymerized with one or more aromatic or non-aromatic non-siloxy-basedmonomers, hydrophobic monomers, hydrophilic monomers or a combinationthereof to produce polymeric compositions of the present invention.

Examples of aromatic and non-aromatic non-siloxy-based monomers usefulfor copolymerization with one or more aromatic-based silyl monomers ofthe present invention include for example but are not limited to2-phenyoxyethyl methacrylate, 3,3-diphenylpropyl methacrylate,N,N-dimethylacrylamide, methyl methacrylate, 2-(1-naphthylethyl)methacrylate, glycol methacrylate, 3-phenylpropyl acrylate and2-(2-naphthylethyl) methacrylate but preferably 2-(1-naphthylethyl)methacrylate for increased refractive index.

Examples of hydrophobic monomers useful for copolymerization with one ormore aromatic-based silyl monomers of the present invention include forexample but are not limited to 2-ethylhexyl methacrylate,3-methacryloyloxypropyldiphenylmethylsilane and 2-phenyloxyethylmethacrylate but preferably 3-methacryloyloxypropyldiphenylmethylsilanefor increased refractive index.

Examples of hydrophilic monomers useful for copolymerization with one ormore aromatic-based silyl monomers of the present invention include forexample but are not limited to N,N-dimethylacrylamide and methylmethacrylate but preferably N,N-dimethylacrylamide for increasedhydrophilicity.

The physical and mechanical properties of copolymers produced fromformulations based on 3-phenylpropyl acrylate (PPA),N,N-dimethylacrylamide (DMA), 3-acryloyloxypropyldiphenylmethylsilane(APDMS) and methyl methacrylate (MMA) with are set forth below in Table1.

TABLE 1 Mechanical and Physical Property Results of formulations basedon PPA, DMA and APDMS (initiator Irgacure ™ 819 at 0.5% (Ciba-Geigy,Basel, Switzerland) and UV blocker at 0.25% for all formulations) ModTear % % Composition W/W % R.I. (g/mm²) (g/mm) % Elong. Rec. H₂OPPA/DMA/APDMS/ 75/25/0/20/1 1.5349 5.1 Hex/Eg/819 75/25/0/20/2 1.5364 55 24 197 88 6.5 75/25/0/20/3 86 5.0 65/25/10/20/1 1.5396  50 47 338 804.5 65/25/10/20/2 1.5442  81 54 228 77 5 65/25/10/20/3 1.5448 143 57 17872 5.7 55/25/20/20/1 1.5409  94 79 332 70 5.5 55/25/20/20/2 1.5429 14177 232 64 4.8 55/25/20/20/3 1.5422 196 83 184 60 5 Hex = Hexanol Eg =EGDMA = Ethyleneglycol dimethacrylate 819 = Irgacure ™ 819

No water content, low water content of less than 15 percent watercontent by volume and high water content “hydrogels” of 15 percent orhigher water content by volume polymeric compositions of the presentinvention having ideal physical characteristics for use in themanufacture of ophthalmic devices are described herein. In theproduction of such polymeric compositions of the present invention, oneor more silyl monomers of the present invention may be polymerized orcopolymerized to form crosslinked three-dimensional networks. However,one or more crosslinking agents may be added in quantities less than 10percent weight per volume (W/V) to the silyl monomer(s), if desired,prior to polymerization or copolymerization thereof.

Examples of suitable crosslinking agents include but are not limited todiacrylates and dimethacrylates of triethylene glycol, butylene glycol,neopentyl glycol, hexane-1,6-diol, thio-diethylene glycol and ethyleneglycol, trimethylolpropane triacrylate, N,N′-dihydroxyethylenebisacrylamide, diallyl phthalate, triallyl cyanurate, divinylbenzene;ethylene glycol divinyl ether, N,N′-methylene-bis-(meth)acrylamide,sulfonated divinylbenzene and divinylsulfone.

Although not required, silyl monomers within the scope of the presentinvention may optionally have one or more strengthening agents addedthereto prior to polymerization or copolymerization thereof, preferablyin quantities of less than about 80 weight percent but more typicallyfrom about 20 to about 60 weight percent.

Examples of suitable strengthening agents are described in U.S. Pat.Nos. 4,327,203, 4,355,147 and 5,270,418, each incorporated herein in itsentirety by reference. Specific examples, not intended to be limiting,of such strengthening agents include cycloalkyl acrylates andmethacrylates, such as for example tert-butylcyclohexyl methacrylate andisopropylcyclopentyl acrylate.

One or more ultraviolet light absorbers may optionally be added to thesubject silyl monomers prior to polymerization or copolymerizationthereof in quantities typically less than 2 percent W/V. Suitableultraviolet light absorbers for use in the present invention include forexample but are not limited to β-(4-benzotriazoyl-3-hydroxyphenoxy)ethylacrylate, 4-(2-acryloyloxyethoxy)-2-hydroxybenzophenone,4-methacryloyloxy-2-hydroxybenzophenone,2-(2′-methacryloyloxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-5′-methacryloyloxyethylphenyl)-2H-benzotriazole,2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-(3″-dimethylvinylsilylpropoxy)-2′-hydroxyphenyl]-5-methoxybenzotriazole,2-(3′-allyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole,and2-[3′-tert-butyl-2′-hydroxy-5′-(3″-methacyloyloxypropoxy)phenyl]-5-chlorobenzotriazolewherein β-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate is thepreferred ultraviolet light absorber.

The silyl monomers of the present invention may be readily cured in castshapes, as discussed in more detail below, by one or more conventionalmethods. Such methods include for example but are not limited toultraviolet light polymerization, visible light polymerization,microwave polymerization, thermal polymerization, free radical thermalpolymerization or combinations thereof.

One or more suitable free radical thermal polymerization initiators maybe added to the monomers of the present invention. Examples of suchinitiators include for example but are not limited to organic peroxides,such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoylperoxide, benzoyl peroxide, tert-butyl peroxypivalate,peroxydicarbonate, and the like. Preferably such an initiator isemployed in a concentration of approximately 0.01 to 1 percent by weightof the total monomer mixture.

Representative ultraviolet light initiators include those known in thefield such as for example but not limited to benzoin methyl ether,benzoin ethyl ether, Darocur™ 1173, 1164, 2273, 1116, 2959, 3331 (EMIndustries) and Irgacur™ 651 and 184 (Ciba-Geigy, Basel, Switzerland).

The polymeric compositions of the present invention are of relativelyhigh refractive index, relatively high elongation and relatively highclarity. The polymeric compositions of the present invention with thedesirable physical properties noted above are particularly useful in themanufacture of ophthalmic devices such as but not limited to relativelythin, foldable intraocular lens implants, contact lenses and cornealinlays.

IOLs having relatively thin optic portions are critical in enabling asurgeon to minimize surgical incision size. Keeping the surgicalincision size to a minimum reduces intraoperative trauma andpostoperative complications. A relatively thin IOL optic portion is alsocritical for accommodating certain anatomical locations in the eye suchas the anterior chamber and the ciliary sulcus. IOLs may be placed inthe anterior chamber for increasing visual acuity in either aphakic orphakic eyes, or placed in the ciliary sulcus for increasing visualacuity in phakic eyes.

The polymeric compositions of the present invention have the flexibilityrequired to allow implants manufactured from the same to be folded ordeformed for insertion into an eye through the smallest possiblesurgical incision, i.e., 3.5 mm or smaller. It is unexpected that thesubject polymeric compositions could possess the ideal physicalproperties described herein. The ideal physical properties of thesubject polymeric compositions are unexpected because high refractiveindex monomers typically lend to polymers that have increasedcrystallinity and decreased clarity, which does not hold true in thecase of the subject polymeric compositions.

The subject silyl monomers and polymeric compositions produced therefromare described in still greater detail in the examples that follow.

EXAMPLE 1 Three-step Synthesis of3-acryloyloxypropydiphenyl-methylsilane (APDMS) Step one: Synthesis of3-(trimethylsilyloxy)propyldiphenylmethylsilane

In a two liter acid washed round bottom flask equipped with magnesiumstirrer, condenser and dry air tube was placed 100 g ofdiphenylmethylsilane, (0.5042 moles), 656.7 g of trimethylsilylallyl(TMS-allyl) alcohol (5.042 moles) and 1000 μl of Pt catalyst (AldrichChemical Co. 47,951-9). The solution was refluxed for 16 hours, cooledto room temperature and 20g of silica gel was added. Stirring wascontinued for 2 hours. The mixture was filtered and rotovapped to oil.The oil was vacuum distilled (boiling point (b.p.) 110–15° C. at 0.1 mmHg). Recovered 158 g (GC-97%) yield 95%.

Step two: Synthesis of 3-hydroxypropyldiphenylmethylsilane

In a one liter erylenmeyer flask was placed 161 g of the product fromstep one above (0.4901 mole) dissolved in 700 ml of methanol. To theabove was slowly added 35 ml of distilled water followed by 4 ml ofglacial acetic acid. This solution was stirred for 2 hours. The solutionwas rotovapped to remove the methanol; re-dissolved in chloroform,washed with distilled water three times, dried over magnesium sulfateand filtered. The solution was rotovapped to a clear oil. Recovered 132g (GC purity 93%).

Step three: Synthesis of 3-acryloyloxypropyldiphenylmethylsilane

In a two liter round bottom flask equipped with mechanical stirrer,dropping funnel, thermometer, condenser and N₂ blanket was placed 132 g(0.4758 mole) of the deprotected alcohol, 53.6 g (0.53 moles) oftriethylamine and 1000 ml of anhydrous ethyl acetate. This solution wascooled to 0° C. and 47g (0.5234 moles) of acryloyl chloride was addeddropwise, keeping the temperature less than 5° C. After the addition wascomplete, the reaction was allowed to come to room temperature andstirred under N₂ overnight. The next morning the solution was washedthree times with cold 2N HCl, one time with brine and one time with 5%NaHCO₃. The resulting solution was dried over MgSO₄, filtered androtovapped to a yellow oil. The oil was passed through a 400 g silicacolumn eluding with 70/30, 50/50 and 30/70 heptane/dichloromethanesolutions (2 bed volumes each). After solvent removal, 59 g of3-acryloyloxypropyldiphenylmethylsilane (98.6% by GC) was recovered.

Synthesis of 2-(1-napthalylethyl) Methacrylate

In a two liter amber colored round bottom flask equipped with mechanicalstirrer, dropping funnel, thermometer, condenser, and N₂ blanket wasplaced 50 g (0.2905 mole) of 1-naphthaleneethanol, 31.4 g (0.31 mole) oftriethylamine and 1000 ml of ethyl acetate. The above was cooled to lessthan 0° C. and 31.9 g (0.305 mole) of methacryloyl chloride was addeddropwise keeping the temperature less than 0° C. The reaction wasallowed to come to room temperature and stirred under N₂ overnight. Thefollowing morning, the organic layer was washed two times with 1N HCl,one time with brine, and two times with 5% NaHCO₃. The organic layer wasdried over MgSO₄, filtered and rotovapped to an oil, and passed through200 g of silica gel eluding with 70/30 heptane/dichloromethane. Aftersolvent removal, recovered 48 g (GC purity 97%).

EXAMPLE 2

To 65 parts of 3-phenylpropyl acrylate (PPA) was added 25 parts ofN,N-dimethylacrylamide, 20 parts of hexanol, 10 parts of APDMS, 3 partsof ethyleneglycol dimethacrylate and 0.5% of Irgacure™ 819 as the UVphotoinitiator and 0.25% of a commercial triazole UV blocker (AldrichChemical Co). The clear solution was sandwiched between two silanizedglass plates using metal gaskets and exposed to UV radiation for twohours. The resultant films were released and extracted in isopropanol(IPA) for four hours, followed by air-drying and a 30 mm vacuum toremove the IPA. The resultant film was hydrated at room temperatureovernight in borate buffered saline. The clear tack-free films possesseda modulus of 81 g/mm², a tear strength of 77 g/mm, a % elongation of228%, a water content of 5% and a refractive index of 1.5442.

EXAMPLE 3

To 70 parts of APDMS was added 10 parts of N,N-dimethylacrylamide, 20parts of hexanol, 1 part of ethyleneglycol dimethacrylate and 0.5% ofIrgacure™ 819 as the UV photoinitiator and 0.25% of a commercialtriazole UV blocker (Aldrich Chemical Co). The clear solution wassandwiched between two silanized glass plates using metal gaskets andexposed to UV radiation for two hours. The resultant films were releasedand extracted in IPA for four hours, followed by air-drying and a 30 mmvacuum to remove the IPA. The resultant film was hydrated at roomtemperature overnight in borate buffered saline. The clear tack-freefilms possessed a modulus of 161 g/mm², a tear strength of 64 g/mm, a %elongation of 183%, a water content of 10.5% and a refractive index of1.517.

Ophthalmic devices such as but not limited to IOLs manufactured usingthe polymeric compositions of the present invention can be of any designcapable of being rolled or folded for implantation through a relativelysmall surgical incision, i.e., 3.5 mm or less. For example, ophthalmicdevices such as IOLs typically comprise an optic portion and one or morehaptic portions. The optic portion reflects light onto the retina andthe permanently attached haptic portions hold the optic portion inproper alignment within an eye. The haptic portions may be integrallyformed with the optic portion in a one-piece design or attached bystaking, adhesives or other methods known to those skilled in the art ina multipiece design.

The subject ophthalmic devices, such as for example IOLs, may bemanufactured to have an optic portion and haptic portions made of thesame or differing materials. Preferably, in accordance with the presentinvention, both the optic portion and the haptic portions of the IOLsare made of one or more polymeric compositions of the present invention.Alternatively however, the IOL optic portion and haptic portions may bemanufactured from differing materials and/or differing polymericcompositions of the present invention, such as described in U.S. Pat.Nos. 5,217,491 and 5,326,506, each incorporated herein in its entiretyby reference. Once the particular material or materials are selected,the same is either cast in molds of the desired shape or cast in theform of rods and lathed or machined into disks. If cast in the form ofrods and lathed or machined into disks, the disks are lathed or machinedinto IOLs at low temperatures below the glass transition temperature(s)of the material(s). The IOLs, whether molded or machined/lathed, arethen cleaned, polished, packaged and sterilized by customary methodsknown to those skilled in the art.

In addition to IOLs, the polymeric compositions of the present inventionare also suitable for use in the manufacture of other ophthalmic devicessuch as but not limited to contact lenses, keratoprostheses, capsularbag extension rings, corneal inlays, corneal rings or like devices.

IOLs manufactured using the unique polymeric compositions of the presentinvention are used as customary in the field of ophthalmology. Forexample, in a surgical procedure, an incision is placed in the cornea ofan eye. Most commonly, through the corneal incision the natural lens ofthe eye is removed (aphakic application) such as in the case of acataractous natural lens. An IOL is then inserted into the anteriorchamber, posterior chamber or lens capsule of the eye prior to closingthe incision. However, the subject ophthalmic devices may be used inaccordance with other surgical procedures known to those skilled in thefield of ophthalmology.

While there is shown and described herein monomers and polymericcompositions, methods of producing the monomers and polymericcompositions, methods of producing ophthalmic devices using thepolymeric compositions and methods of using ophthalmic devicesmanufactured from the polymeric compositions, all in accordance with thepresent invention, it will be manifest to those skilled in the art thatvarious modifications may be made without departing from the spirit andscope of the underlying inventive concept. The present invention islikewise not intended to be limited to particular devices describedherein except insofar as indicated by the scope of the appended claims.

1. Aromatic-based silyl monomers having a structure represented by

wherein R is a polymerizable group selected from the group consisting ofacrylamido, methacrylamido, itaconate, fumaroyl, vinyl carbamate, andvinyl carbonate; X is selected from the group consisting of C₁₋₁₀alkylene, C₆₋₃₆ alkyleneoxy, C₆₋₃₆ arylene, and C₆₋₃₆ aryleneoxy; andthe R₁ groups are the same or different, and are selected from the groupconsisting of C₁₋₁₀ alkyl, C₁₋₂₀ cycloalkyl, C₆₋₃₆ aryl, C₆₋₃₆ arylether, C₆₋₃₆ heterocycle, C₆₋₃₆ heterocycle with one or moresubstituents, C₁₋₁₀ alkyl ether and C₆₋₃₆ aryloxy, with at least one R₁group being other than a methyl group and at least one R₁ group beingnon-phenyl and at least one R₁ group being an aromatic-based group. 2.Aromatic-based silyl monomers having a structure represented by

wherein R is a polymerizable group selected from the group consisting ofacrylamido, methacrylamido, itaconate, fumaroyl, vinyl carbamate, andvinyl carbonate; X is selected from the group consisting of C₁₋₁₀alkylene, C₁₋₁₀ alkyleneoxy, C₆₋₃₆ arylene, and C₆₋₃₆ aryleneoxy; andthe R₁ groups are the same or different, and are selected from the groupconsisting of C₁₋₁₀ alkyl, C₁₋₂₀ cycloalkyl, naphthyl, C₆₋₃₆ aryl ether,C₆₋₃₆ heterocycle, C₆₋₃₆ heterocycle with one or more substituents,C₁₋₁₀ alkyl ether and C₆₋₃₆ aryloxy; and at least one R₁ group being anaromatic-based group.
 3. Aromatic-based silyl monomers having astructure represented by

wherein R is a polymerizable group selected from the group consisting ofacrylamido, methacrylamido, itaconate, fumaroyl, vinyl carbamate, andvinyl carbonate; X is selected from the group consisting of C₁₋₁₀alkylene, C₁₋₁₀ alkyleneoxy, C₆₋₃₆ arylene, and C₆₋₃₆ aryleneoxy; andthe R₁ groups are different and are selected from the group consistingof C₁₋₂₀ cycloalkyl, C₆₋₃₆ aryl, C₆₋₃₆ aryl ether, C₆₋₃₆ heterocycle,C₆₋₃₆ heterocycle with one or more substituents, C₁₋₁₀ alkyl ether andC₆₋₃₆ aryloxy; and at least one R₁ group being an aromatic-based group.